CN104999071B - A kind of gold nano stick array and its preparation method and application - Google Patents
A kind of gold nano stick array and its preparation method and application Download PDFInfo
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- CN104999071B CN104999071B CN201510354816.9A CN201510354816A CN104999071B CN 104999071 B CN104999071 B CN 104999071B CN 201510354816 A CN201510354816 A CN 201510354816A CN 104999071 B CN104999071 B CN 104999071B
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Abstract
The invention discloses a kind of preparation method of gold nano stick array, the method includes：Prepare the gold nanorods aqueous solution that cetyl trimethylammonium bromide (CTAB) is modified, and adjust ultimate density respectively 0.2 0.6nmol/L, 0.5 2mmol/L of gold nanorods, CTAB, and add sulfhydryl compound to stir, obtain mixed solution, and make sulfhydryl compound ultimate density be 0.01 0.2mmol/L, drip on hydrophily planar substrates after above-mentioned mixed solution is concentrated, after natural drying, obtain gold nano stick array.The preparation method of the gold nano stick array is simple to operate, mild condition, prepared gold nano stick array compound with regular structure, and is macroscopic millimeter rank, and its surface has equally distributed SERS " focus ", and facilitating its use as SERS strengthens substrate.Present invention also offers a kind of gold nano stick array and its application.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of gold nano stick array and preparation method thereof and should
With.
Background technology
The even more high power again of Molecular Raman signal enhancing million can be very by SERS (SERS) effect
Chemistry well, biological detecting method.This superelevation enhancing depends primarily on SERS " focus "：It is mainly by surface plasma
Resonance body the adjacent noble metal nano particles as substrate the contact positions such as gap produce with extremely strong local electric field
" point ".When detection molecules are adsorbed in " focus " position, its Raman signal can be greatly enhanced.However, due to detection architecture
The random distribution of interior " focus " position so that the reappearance of SERS detection techniques is restricted.Therefore, prepare a kind of " focus " point
The SERS substrates of cloth uniform, controllable, it is particularly significant in the application aspect of SERS technologies.
Strengthen the one kind in the noble metal nanometer material of substrate as SERS, gold nanorods have special physics respectively to different
Property, such as with the regulation and control to gold nanorods draw ratio, its intrinsic plasma resonance property can be adjusted.And gold nanorods pass through
The assembly that self assembly is obtained shows the performance more excellent than single gold nanorods, such as regulatable obscurity, to each other etc.
Aggregating characteristic that gas ions resonance coupling brings etc., this causes gold nanorods assembly in high sensitive sensor (such as SERS), light
The fields such as electric equipment are widely used.
But the small scale of existing gold nanorods assembly, (as CN103341623 can only obtain several gold nanorods
The assembling of pattern shoulder to shoulder), and the nano-particle assembling of large area (i.e. micron level) can not be realized, when using it for SERS bases
During bottom, structure is taken a walk on substrate discontinuously, overall unordered, necessarily causes " focus " skewness.
In view of this, it is necessary to which a kind of extensive and regular gold nano stick array of array structure and preparation method thereof is provided
And application.
The content of the invention
Based on above-mentioned technical problem, the invention provides a kind of gold nano stick array and its preparation method and application, described
The scale of gold nano stick array is in macroscopic grade, and compound with regular structure, and the gold nano stick array is increasing as SERS
During strong basis bottom, its surface has equally distributed SERS " focus ", strengthens ability high, reproducible.The gold nano stick array
Preparation method is simple to operate, mild condition.
In a first aspect, the invention provides a kind of preparation method of gold nano stick array, comprises the following steps：
(1) aqueous solution of the gold nanorods of cetyl trimethylammonium bromide modification is prepared, and by being centrifuged, removing supernatant
Liquid, then disperseed with pure water, obtain dispersion liquid of gold nanorods that concentration is 0.2-0.6nmol/L；
(2) dispersion liquid of the gold nanorods is centrifuged, and cetyl three is added toward the precipitation after centrifugation
Methyl bromide ammonium, obtains gold nanorods twice dispersing liquid, and the cetyl trimethylammonium bromide is secondary in the gold nanorods
Concentration in dispersion liquid is 0.5-2mmol/L；
(3) sulfhydryl compound is added in the gold nanorods twice dispersing liquid, obtain three dispersion liquids of gold nanorods, so
Afterwards by three dispersion liquids of gold nanorods stirred overnight at room temperature, wherein, the sulfhydryl compound is in the gold nanorods
Concentration in three dispersion liquids is 0.01-0.2mmol/L, and the sulfhydryl compound includes (11- mercapto-undecanoic bases) six (second two
Alcohol)；
(4) three dispersion liquids of the gold nanorods are carried out into centrifugal concentrating, obtains three dispersion liquids of gold nanorods for concentrating；
(5) by the surface of three dispersant liquid drops of gold nanorods of concentration to hydrophily planar substrates, using solvent evaporated method
It is dried, obtains gold nano stick array.
Preferably, in step (1), the aqueous solution of the gold nanorods for preparing cetyl trimethylammonium bromide modification
Method is seed mediated growth method.
Preferably, in step (1), the rotating speed of the centrifugation is 8000-12000r/min.
Preferably, in step (1), a length of 30-70nm of rod of the gold nanorods, its draw ratio are 3-5.
As described in the present invention, it is in step (1), described to prepare the Jenner that cetyl trimethylammonium bromide (CTAB) is modified
The method of the aqueous solution of rice rod, can adopt the conventional method of this area to carry out, for example, can be given birth to the crystal seed of wet chemistry synthesis
Regular way and non-crystal seed growth method etc. are using seed mediated growth method etc..
As described in the present invention, in the aqueous solution of the gold nanorods modified using CTAB obtained in said method, CTAB
Concentration be generally 0.5-2mol/L, outside scope of protection in step of the present invention (2), therefore, the present invention is toward the gold
CTAB is added in dispersion liquid of nanometer rods, makes concentration of the CTAB in the gold nanorods twice dispersing liquid be 0.5-
2mmol/L, and concentration of the gold nanorods in the gold nanorods twice dispersing liquid is still 0.2-0.6nmol/L.
Preferably, the volume of dispersion liquid of gold nanorods described in step (1) and gold nanorods described in step (2)
The volume of twice dispersing liquid is identical.
As described in the present invention, in step (2), the cetyl trimethylammonium bromide (CTAB) is in the gold nanorods
Concentration in twice dispersing liquid refers to the concentration of the CTAB being dissolved in water.
Preferably, in step (2), the rotating speed 8000-12000r/min of the centrifugation.
Preferably, in step (3), sulfhydryl compound is added in the twice dispersing liquid to gold nanorods, specially：Will be dense
The aqueous solution of sulfhydryl compound for 0.1-0.4mmol/L is spent by 1:2 ratio and gold nanorods twice dispersing obtained by step (2)
Liquid is mixed.
Preferably, in step (4), three dispersion liquids of gold nanorods of the concentration are three dispersion liquids of the gold nanorods
10-75 times of concentration.
Preferably, in step (5), the hydrophily planar substrates include that polished silicon slice, surface have the silicon of silicon dioxide layer
Piece, surface have the sheet glass of silicon dioxide layer and surface to have the quartz plate of silicon dioxide layer.
Preferably, in step (5), the solvent evaporated method is dried, and refers to the gold nanorods three times that surface drop is had concentration
The planar substrates horizontal stationary of dispersion liquid is the environment of 40%-95% in air humidity, treats that the natural drying of substrate surface liquid is
Only.
Preferably, in step (5), the gold nano stick array is by the compact arranged list in the longitudinal direction for being laid in substrate surface
Layer gold nanorods constitute, in the gold nano stick array, a length of 30-70nm of rod of gold nanorods, its draw ratio be 3-5, Jenner
The interrod spacing of rice rod is 1-3nm.
The gold nano stick array that first aspect present invention is provided preparation method is simple to operate, mild condition, can be effective
Realize the efficient self assembly of gold nanorods, prepared gold nano stick array compound with regular structure is macroscopic millimeter rank,
Gold nano stick array is conducive to strengthen substrate as SERS.
Second aspect, the invention provides a kind of gold nano stick array, the gold nano stick array is using the present invention the
On the one hand the preparation method described in is obtained.
Preferably, the gold nano stick array is by the compact arranged gold nanorods structure in the longitudinal direction for being laid in substrate surface
Into, in the gold nano stick array, a length of 30-70nm of rod of gold nanorods, its draw ratio be 3-5, the interrod spacing of gold nanorods
For 1-3nm.
The third aspect, the invention provides the preparation side described in the gold nano stick array or first aspect described in second aspect
Application of the gold nano stick array obtained in method in SERS (SERS) detection.
The application, comprises the following steps：
(1) aqueous solution of the gold nanorods of cetyl trimethylammonium bromide modification is prepared, and by being centrifuged, removing supernatant
Liquid, then disperseed with pure water, obtain dispersion liquid of gold nanorods that concentration is 0.2-0.6nmol/L；
(2) dispersion liquid of the gold nanorods is centrifuged, and cetyl three is added toward the precipitation after centrifugation
Methyl bromide ammonium, obtains gold nanorods twice dispersing liquid, and the cetyl trimethylammonium bromide is secondary in the gold nanorods
Concentration in dispersion liquid is 0.5-2mmol/L；
(3) sulfhydryl compound is added in the gold nanorods twice dispersing liquid, obtain three dispersion liquids of gold nanorods, so
Afterwards by three dispersion liquids of gold nanorods stirred overnight at room temperature, wherein, the sulfhydryl compound is in the gold nanorods
Concentration in three dispersion liquids is 0.01-0.2mmol/L, and the sulfhydryl compound includes (11- mercapto-undecanoic bases) six (second two
Alcohol)；
(4) three dispersion liquids of the gold nanorods are carried out into centrifugal concentrating to 10-75 times, obtains the gold nanorods three for concentrating
Secondary dispersion liquid；
(5) by the surface of three dispersant liquid drops of gold nanorods of concentration to hydrophily planar substrates, using solvent evaporated method
It is dried, obtains gold nano stick array；
(6) determinand solution is added dropwise on the surface of above-mentioned gold nano stick array, carries out Raman spectrum test.
Preferably, in step (6), it is described carry out Raman spectrum test when, the excitation wavelength for using be 633nm or 785nm.
As described in the present invention, in step (6), the volume of determinand solution should be less than the body of gold nano stick array
Product.
Preferably, in step (6), the volume of determinand solution is 0.5-2 μ l.
The concentration of determinand solution is not particularly limited.
The gold nano stick array that the present invention is prepared uniformly divides as its surface has when substrate is strengthened as SERS
The SERS " focus " of cloth, it is not only high to the enhancing ability of determinand, and also the reappearance for detecting might as well.Also by gold nano stick array
For the SERS in the fields such as food analysis, environmental analysis, Pharmaceutical Analysis, chemical analysis and bioanalysis
(SERS) detect.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described.Specific embodiment described herein is only to explain this
It is bright, it is not intended to limit the present invention.
Fig. 1 is the transmission electron microscope of the gold nanorods that six alkyl trimethyl ammonium bromides (CTAB) are modified in embodiment 1
(TEM) photo；
Fig. 2 is the ultraviolet-visible absorption spectroscopy of the gold nanorods before and after assembling in embodiment 1；
Fig. 3 is the photo in kind of gold nano stick array obtained in embodiment 1；
Fig. 4 is SEM (SEM) photo (top view) of gold nano stick array obtained in embodiment 1；
Fig. 5 is that the gold nano stick array described in embodiment 1 is used to detect as surface reinforced Raman active (SERS) substrate
The Raman detection result of malachite green；
Fig. 6 is the TEM photos of the gold nanorods of CTAB modifications in embodiment 2；
Fig. 7 is the SEM photograph (top view) of gold nano stick array obtained in embodiment 2；
Fig. 8 is the SEM photograph (side view) of gold nano stick array obtained in embodiment 2.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
A kind of preparation method of gold nano stick array, comprises the following steps：
(1) the water-soluble of the gold nanorods that cetyl trimethylammonium bromide (CTAB) is modified is prepared using gold seeds growth method
Liquid, it is specific as follows：
The synthesis of a, gold seeds：The gold chloride of the 0.0005M of 2.5mL is dissolved in the CTAB solution of the 0.2mol/L of 2.5mL
In, it is well mixed, 0.3mL is newly configured, the sodium borohydride solution of the 0.01M of precooling is quickly added in above-mentioned solution, strength is mixed
2min is closed, and 2h is placed at 25 DEG C of room temperature, is obtained gold seeds；
The configuration of b, the growth solution of gold nanorods：By the silver nitrate of 0.15mL, 0.004mol/L, the chlorine of 5mL, 0.001M
Auric acid solution is added in the CTAB of 5mL, 0.2mol/L, is subsequently adding the sodium ascorbate of the 0.0788M of 70 μ L, is fully reduced
2min, the gold seeds for adding 12 μ L above-mentioned steps (a) to configure, after being sufficiently stirred for 20s, obtain mixed solution, and stand in 25 DEG C
It is stand-by；
And above-mentioned mixed solution resuspended 2-3 time (be centrifuged, remove supernatant by being centrifuged under the rotating speed of 10000rpm/min
Liquid, then disperseed with 10ml pure water), unnecessary reaction residue is removed, the gold nanorods that concentration is 0.4nmol/L is obtained and is once divided
Dispersion liquid；
(2) dispersion liquid of the gold nanorods is centrifuged, wherein centrifugal speed be 12000rpm/min, and toward from
Cetyl trimethylammonium bromide is added in precipitation after the heart, the gold nanorods twice dispersing liquid of 10ml is obtained, the CTAB exists
Concentration in the gold nanorods twice dispersing liquid is 1.2mmol/L；
(3) (11- mercapto-undecanoic bases) six (ethylene glycol) aqueous solution by concentration for 0.2mmol/L presses 1:2 ratio with
Gold nanorods twice dispersing liquid mixing obtained by step (2), and stirred overnight at room temperature, obtain three dispersion liquids of gold nanorods,
Wherein, concentration of described (11- mercapto-undecanoic bases) six (ethylene glycol) in three dispersion liquids of the gold nanorods is
0.1mmol/L；
(4) three dispersion liquids of the gold nanorods are carried out into centrifugal concentrating to 50 times, obtains the gold nanorods three times for concentrating
Dispersion liquid；
(5) by the silicon chip of three dispersant liquid drops of gold nanorods of concentration to polishing, it is dried using solvent evaporated method, and will
Silicon wafer horizontal is still in the environment that air humidity is 80%, till treating that substrate surface liquid is spontaneously dried, obtains gold nanorods battle array
Row.
Fig. 1 is the transmission electricity of dispersion liquid of gold nanorods of CTAB modifications obtained in step (1) in the embodiment of the present invention 1
Mirror figure (TEM), it will be seen from figure 1 that the particle diameter of the gold nanorods is than more uniform, monodispersity is good, a length of 65nm of rod, its
Draw ratio is 3.5.
Fig. 2 be the embodiment of the present invention 1 in assemble before and after gold nanorods uv-visible absorption spectra, in figure " from group
Gold nanorods before dress " refer to dispersion liquid of gold nanorods of CTAB modifications, and " gold nanorods after self assembly " refer to step
(3) three dispersion liquids of gold nanorods obtained in, figure it is seen that the absworption peak of " gold nanorods before self assembly " is mainly concentrated
It is at the peak centered on 810nm, few in the absworption peak of 500nm or so, and the absworption peak of the gold nanorods after self assembly is located at
540nm, 650nm or so, this major surfaces dressing agent for being likely due to gold nanorods become (11- sulfydryls 11 by CTAB
Alkyl) six (ethylene glycol), therefore absworption peak has movement.
In kind photo figures of the Fig. 3 for gold nano stick array obtained in the embodiment of the present invention 1, Fig. 3 reflect the gold nanorods
The macro morphology of array；Scanning electron microscope diagrams (SEM, top view) of the Fig. 4 for gold nano stick array, it is as can be seen from Figure 4, described
The compound with regular structure of gold nano stick array, the gold nano stick array are by the compact arranged gold nano in the longitudinal direction for being laid in substrate surface
Bar construction, the gold nanorods are arranged perpendicular to substrate surface, a length of 65nm of rod of gold nanorods, and its draw ratio is 3.5, Jenner
The interrod spacing of rice rod is 2nm.The gold nano stick array it is structurally ordered, regular, substrate can be strengthened as SERS, its surface has
There is equally distributed SERS " focus ".
Application Example 1
Gold nano stick array obtained in above-described embodiment 1 is used for SERS strengthens substrate, for detecting malachite green, specifically
For：
Gold nano stick array obtained in 1 step of Example (5), the gold nano stick array surface drip 5 μ L, 10-6mol/L
The malachite green aqueous solution, after its drying after, carry out Raman spectrum test.
It is 633nm that Raman tests used optical maser wavelength, and integral number of times is 1 time.
Simultaneously in order to project the effect of the present invention, comparable sodium, unassembled gold nanorods are also served as into SERS substrates, it is right
10-6The malachite green aqueous solution of mol/L carries out Raman spectrum test.
The result of Raman test is as shown in Figure 5：As ise apparent from FIG. 5, when the gold nano stick array that assembling is formed is used for
During SERS substrates (a in Fig. 5), active with very high SERS, the more unassembled gold nanorods of its intensification factor (b in Fig. 5) are about
It is high 5 times.
Embodiment 2
A kind of preparation method of gold nano stick array, comprises the following steps：
(1) the water-soluble of the gold nanorods that cetyl trimethylammonium bromide (CTAB) is modified is prepared using gold seeds growth method
Liquid, it is specific as follows：
In the test tube or beaker of 50mL, add the chlorauric acid solution of 1mL, 5mM, the CTAB aqueous solution for taking 5mL, 0.2M to add
Enter wherein, gentle agitation, addition 4.5mL ultra-pure waters, the sodium oleate solution of 500 μ L, 0.1M, the silver nitrate solution of 250 μ L, 4mM,
Gentle agitation, adds 8 μ L, 37% concentrated hydrochloric acid, gentle agitation to add the 56 μ L of ascorbic acid of 0.1M, gentle agitation to treat solution
Fade to colourless, rapidly join the sodium borohydride solution of 15 μ L, 0.01M, 2～3h is stood in 35 DEG C of insulating boxs, mixing is obtained molten
Liquid；
And above-mentioned mixed solution resuspended 2-3 time (be centrifuged, remove supernatant by being centrifuged under the rotating speed of 12000rpm/min
Liquid, then disperseed with 10ml pure water), unnecessary reaction residue is removed, the gold nanorods that concentration is 0.6nmol/L is obtained and is once divided
Dispersion liquid；
(2) dispersion liquid of the gold nanorods is centrifuged, wherein centrifugal speed be 8000rpm/min, and toward from
Cetyl trimethylammonium bromide is added in precipitation after the heart, the gold nanorods twice dispersing liquid of 10ml is obtained, the CTAB exists
Concentration in the gold nanorods twice dispersing liquid is 2mmol/L；
(3) (11- mercapto-undecanoic bases) six (ethylene glycol) aqueous solution by concentration for 0.4mmol/L presses 1:2 ratio with
Gold nanorods twice dispersing liquid mixing obtained by step (2), and stirred overnight at room temperature, obtain three dispersion liquids of gold nanorods,
Wherein, concentration of described (11- mercapto-undecanoic bases) six (ethylene glycol) in three dispersion liquids of the gold nanorods is
0.2mmol/L；
(4) three dispersion liquids of the gold nanorods are carried out into centrifugal concentrating to 75 times, obtains the gold nanorods three times for concentrating
Dispersion liquid；
(5) three dispersant liquid drops of gold nanorods of concentration are had on the silicon chip of silicon dioxide layer to surface, using solvent
Evaporation is dried, and is that above-mentioned silicon wafer horizontal is still in the environment that air humidity is 95%, treats that substrate surface liquid is done naturally
After dry, gold nano stick array is obtained.
Fig. 6 is the transmission electricity of dispersion liquid of gold nanorods of CTAB modifications obtained in step (1) in the embodiment of the present invention 2
Mirror figure (TEM), from fig. 6, it can be seen that the particle diameter of the gold nanorods is than more uniform, monodispersity is good, a length of 30nm of rod, its
Draw ratio is 3；Fig. 7, Fig. 8 are respectively the SEM photograph (top view) of gold nano stick array obtained in embodiment 2, SEM photograph (side
View), as can be seen from Figure 7, the compound with regular structure of the gold nano stick array, the gold nano stick array are by being laid in substrate surface
The compact arranged gold nanorods in longitudinal direction constitute, as can be seen from Figure 8, gold nanorods are arranged perpendicular to substrate surface, constitute gold
Nanometer stick array, in the gold nano stick array, a length of 30nm of rod of gold nanorods, its draw ratio are 3, between the rod of gold nanorods
Away from for 3nm.
Application Example 2
Gold nano stick array obtained in above-described embodiment 2 is used for SERS strengthens substrate, for detecting malachite green, specifically
For：
Gold nano stick array obtained in 2 step of Example (5), the gold nano stick array surface drip 5 μ L, 10-5mol/L
The malachite green aqueous solution, after its drying after, carry out Raman spectrum test.
It is 633nm that Raman tests used optical maser wavelength, and integral number of times is 1 time.
When the gold nano stick array is used for SERS substrates, active with very high SERS, its intensification factor is more unassembled
Gold nanorods it is about high 4 times.
Embodiment 3
A kind of preparation method of gold nano stick array, comprises the following steps：
(1) the water-soluble of the gold nanorods that cetyl trimethylammonium bromide (CTAB) is modified is prepared using gold seeds growth method
Liquid, it is specific as follows：
The synthesis of a, gold seeds：The gold chloride of the 0.0005M of 2.5mL is dissolved in the CTAB solution of the 0.2mol/L of 2.5mL
In, it is well mixed, 0.3mL is newly configured, the sodium borohydride solution of the 0.01M of precooling is quickly added in above-mentioned solution, strength is mixed
2min is closed, and 2h is placed at 25 DEG C of room temperature, is obtained gold seeds；
The configuration of b, the growth solution of gold nanorods：By the silver nitrate of 0.10mL, 0.004mol/L, the chlorine of 5mL, 0.001M
Auric acid solution is added in the CTAB of 5mL, 0.2mol/L, is subsequently adding the sodium ascorbate of the 0.0788M of 70 μ L, is fully reduced
2min, the gold seeds for adding 10 μ L above-mentioned steps (a) to configure, after being sufficiently stirred for 20s, obtain mixed solution, and stand in 25 DEG C
It is stand-by；
And above-mentioned mixed solution resuspended 2-3 time (be centrifuged, remove supernatant by being centrifuged under the rotating speed of 8000rpm/min
Liquid, then disperseed with 10ml pure water), unnecessary reaction residue is removed, the gold nanorods that concentration is 0.2nmol/L is obtained and is once divided
Dispersion liquid；
(2) dispersion liquid of the gold nanorods is centrifuged, wherein centrifugal speed be 10000rpm/min, and toward from
Cetyl trimethylammonium bromide is added in precipitation after the heart, the gold nanorods twice dispersing liquid of 10ml is obtained, the CTAB exists
Concentration in the gold nanorods twice dispersing liquid is 0.5mmol/L；
(3) (11- mercapto-undecanoic bases) six (ethylene glycol) aqueous solution by concentration for 0.1mmol/L presses 1:2 ratio with
Gold nanorods twice dispersing liquid mixing obtained by step (2), and stirred overnight at room temperature, obtain three dispersion liquids of gold nanorods,
Wherein, concentration of described (11- mercapto-undecanoic bases) six (ethylene glycol) in three dispersion liquids of the gold nanorods is
0.01mmol/L；
(4) three dispersion liquids of the gold nanorods are carried out into centrifugal concentrating to 10 times, obtains the gold nanorods three times for concentrating
Dispersion liquid；
(5) three dispersant liquid drops of gold nanorods of concentration are had on the quartz plate of silicon dioxide layer to surface, using solvent
Evaporation is dried, and is, in the environment that air humidity is 40%, to treat substrate surface liquid nature by above-mentioned quartz plate horizontal stationary
It is dried, obtains gold nano stick array.
Gold nano stick array obtained in embodiment 3 is by the compact arranged individual layer gold nano in the longitudinal direction for being laid in substrate surface
Bar construction, in the gold nano stick array, a length of 70nm of rod of gold nanorods, its draw ratio 5, the interrod spacing of gold nanorods is
1nm。
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of gold nano stick array, it is characterised in that comprise the following steps：
(1) aqueous solution of the gold nanorods of cetyl trimethylammonium bromide modification is prepared, and by being centrifuged, removing supernatant, then
Disperseed with pure water, obtain dispersion liquid of gold nanorods that concentration is 0.2-0.6nmol/L；
(2) dispersion liquid of the gold nanorods is centrifuged, and cetyl trimethyl is added toward the precipitation after centrifugation
Ammonium bromide, obtains gold nanorods twice dispersing liquid, and the cetyl trimethylammonium bromide is in the gold nanorods twice dispersing
Concentration in liquid is 0.5-2mmol/L, and concentration of the gold nanorods in the gold nanorods twice dispersing liquid is 0.2-
0.6nmol；
(3) sulfhydryl compound is added in the gold nanorods twice dispersing liquid, obtain three dispersion liquids of gold nanorods, then will
Three dispersion liquids of gold nanorods stirred overnight at room temperature, wherein, the sulfhydryl compound is in gold nanorods three times
Concentration in dispersion liquid is 0.01-0.2mmol/L, and the sulfhydryl compound includes (11- mercapto-undecanoic bases) six (ethylene glycol)；
(4) three dispersion liquids of the gold nanorods are carried out into centrifugal concentrating, obtains three dispersion liquids of gold nanorods for concentrating；
(5) by the surface of three dispersant liquid drops of gold nanorods of concentration to hydrophily planar substrates, it is dried using solvent evaporated method,
Obtain gold nano stick array.
2. the preparation method of gold nano stick array as claimed in claim 1, it is characterised in that in step (1), it is described to prepare ten
The method of the aqueous solution of the gold nanorods of six alkyl trimethyl ammonium bromides modification is seed mediated growth method.
3. the preparation method of gold nano stick array as claimed in claim 1, it is characterised in that gold nano described in step (1)
The volume of dispersion liquid of rod is identical with the volume of gold nanorods twice dispersing liquid described in step (2).
4. the preparation method of gold nano stick array as claimed in claim 1, it is characterised in that in step (2), the centrifugation
Rotating speed is 8000-12000r/min.
5. the preparation method of gold nano stick array as claimed in claim 1, it is characterised in that in step (4), the concentration
Three dispersion liquids of gold nanorods are 10-75 times of the concentration of three dispersion liquids of the gold nanorods.
6. the preparation method of gold nano stick array as claimed in claim 1, it is characterised in that in step (5), the hydrophily
Planar substrates include that polished silicon slice, surface have the silicon chip of silicon dioxide layer, surface to have the sheet glass of silicon dioxide layer and surface to have
The quartz plate of silicon dioxide layer.
7. the preparation method of gold nano stick array as claimed in claim 1, it is characterised in that in step (5), the solvent are steamed
The method of sending out is dried, and refers to and by the planar substrates horizontal stationary of three dispersion liquids of gold nanorods that surface drop has concentration in air humidity is
The environment of 40%-95%, till treating that substrate surface liquid is spontaneously dried.
8. the preparation method of gold nano stick array as claimed in claim 1, it is characterised in that in step (5), the gold nano
Rod array is made up of the compact arranged gold nanorods in the longitudinal direction for being laid in substrate surface, in the gold nano stick array, Jenner
The a length of 30-70nm of rod of rice rod, its draw ratio are 3-5, and the interrod spacing of gold nanorods is 1-3nm.
9. a kind of gold nano stick array, it is characterised in that be obtained using the preparation method described in any one of claim 1-5.
10. gold nano stick array obtained in preparation method as claimed in claim 1 is in SERS detection
Using.
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| CN201510354816.9A CN104999071B (en) | 2015-06-24 | 2015-06-24 | A kind of gold nano stick array and its preparation method and application |
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| CN104999071B true CN104999071B (en) | 2017-04-05 |
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| CN110108697B (en) * | 2019-06-25 | 2022-03-08 | 北威(重庆)科技股份有限公司 | Surface-enhanced Raman scattering micro-nano chip, preparation method and application thereof, and Raman spectrum testing system |
| CN110987915B (en) * | 2019-12-03 | 2022-04-01 | 泸州品创科技有限公司 | Method for rapidly identifying Chinese liquor based on gold nanorod colorimetric sensor array |
| CN111060490A (en) * | 2019-12-25 | 2020-04-24 | 安徽中科赛飞尔科技有限公司 | SERS detection method of succinylcholine chloride |
| CN113899732B (en) * | 2021-09-30 | 2023-09-22 | 航天科工(长沙)新材料研究院有限公司 | PH value sensitive ligand modified nano gold and preparation method thereof |
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